Probing the REDOX effect of helical tetraspirobenzene on nonlinear optical properties

AbstractThe helical structure is a classical framework to design high-performance organic electro-optical materials. In this work, the structure-property’s relationships of helical tetraspirobenzene (1) and its oxidation (12+) and reduction (12–) products are explored. The results show that the redox brings some distinctive changes in their geometric structure and electronic property, which regulate the first hyperpolarisability (βtot). Among these structures, the 12– has the largest βtot value of 4.2 × 104, which is greatly larger than 2.0 × 102 a.u. of. 12+. Therefore, the reduction effect is more obvious than the oxidation effect. Furthermore, the UV-Vis absorption spectrum also proves this phenomenon: the oxidation product has a new red-shifted absorption peak (571 nm) and the reduction product has two new red-shifted absorption peaks (577 and 797 nm). We hope the present work can provide theoretical guidance for the search for high-performance nonlinear optical materials by using the redox effect.KEYWORDS: TetraspirobenzeneRedoxNLO property AcknowledgementsYe-Xuan Li: Data curation, Writing – original draft, Writing – review & editing. Hong-Liang Xu: Conceptualisation, Methodology, Writing – review & editing. Zhong-Min Su: Supervision.Disclosure statementNo potential conflict of interest was reported by the author(s).Data availability statementData will be made available on request.Additional informationFundingWe gratefully acknowledge the Natural Science Foundation of Science and Technology Department of Jilin Province [20230101043JC].